Mineral oil composition



Patented Apr. 23, 1940- UNITED STATES txamine PATENT OFFICE MINERAL OILCOMPOSITION Orland M. Reifi, Woodbury, N. J., assignor to Socony-VacuumOil Company, Incorporated, New York, N. Y., a corporation of New York NoDrawing. Application August 3, 1938, Serial No. 222,755

12 Claims.

This invention has to do in a general way with mineral oil compositionsand is more particularly concerned with the production of a mineral oilfraction of the viscous type having an improving agent incorporatedtherein.

It is a primary object of this invention to provide a mineral oilcomposition of the type above referred to which has been improved inseveral related and unrelated properties by a single improving agent.The invention is predicated upon the discovery of a novel class ofimproving agents of multifunctional activity, which may be broadlydescribed as oil-miscible metalorganic compounds or compositionscharacterized by the presence of a wax-substituted aryl nucleus.

I have found that compounds or compositions falling into the abovegeneral class, when blended in a minor proportion with a mineral oilfraction of the lubricant type, are eifective to depress the pour point,improve the viscosity index (V. I.) and inhibit oxidation of the oil. Byinhibiting oxidation these improving agents act to retard the formationof sludge and acidic products of oxidation. They also have a peptizingaction on such sludge as may eventually be formed. Thus the improvingagents contemplated herein, may, for example, be used in internalcombustion engine lubricants to retard or prevent the sticking of pistonrings, the corrosion of bearings (particularly those formed of alloymetals normally susceptible to corrosion)','etc.,-and -at'i'il'fe sametime will act to deprgssthepour point and improue the viscosity index of"the "bfilj rfifoiigh the proper'choi'ceof metal substituents (lead,copper, tin, or zinc for example) the load-carrying capacity orlubricity of the oil may also be improved. This so-called extremepressure (E. P.) value of heavy lubricants may be even further improvedby the presence in these metalorganic compounds of other substituentssuch as sulfur and chlorine.

The use of these improving agents is not confined to lubricating oils,however, but they may be employed in any mineral oil fraction where oneor more of the improved properties recited above is desired.

1/ Although I do not wish to be bound by any theory as to the manner inwhich the improving agents described herein function in a mineral oilfraction, it appears that pour point and V. I. improving properties arederived from the large complex molecular structure obtained fromthe waxor equivalent long chain aliphatic hydrocarbon substituent and theassociated aryl nucleus or nuclei and that the antioxidant propertiesof' long chain aliphatic group or radical derived from some othercompound or material in suflicient amount to render the compostionmiscible with mineral oil under normal conditions of handling and useand a metal or metallo constituent which may be in the form of a metalatom directly attached to the hydrocarbon radical or group or which maybe present as a metallo complex, such as a metal-substituted hydroxy,thiohydroxy,'carboxy, or thiocarboxy group corresponding respec- I.

tively to an oxide, a mercaptide, a metal'carboxylate, or a metal saltof a thio acid such as thiolic or xanthic acid and the like.

Compounds or compositions of the above general character may also bebroadly classified into two groups, depending upon whether the metal ormetallo complex (metallo-oxy, metal carboxylate, metal, etc.) isdirectly attached to the aryl nucleus which carries the wax substituentor is directly attached to a hydrocarbon substituent or substitutedhydrocarbon substituent in the aryl nucleus.

To facilitate the description and illustration of the general class ofcompounds or compositions contemplated herein vas oil-improving. a nts,we may represent these compounds or compositions by the followinggeneral formula:

in which (Wax) molecular radical or group of a predominantly aliphatichydrocarbon material characterized by a relatively long chain molecularstructure .of at least twenty carbon atoms, such as petroleum wax, esterwax, and the like, which radical or group is present asa substituentattached to an aryl nucleus T; n represents the number of wax is'equalto one or. a whole number correspon ing to the number of valences on thearyl nucleus T which are not indicates the characterizing 5osubstituents attached to a single nucleusT. and f' satisfied by residualhym a or othersubstituents T-representsiiramfiatic I hydrocarbon radicalsuch as, for example, one selected from the group comprising monocyclicor polycyclic aryl, alkaryl, hydroxy-aryl, halogenaryl, amino-aryl,nitro-aryl radicals or groupsfdiaryl radicals in which the aryl nucleiare directly connected, diaryl radicals in which the aryl nuclei areconnected through an ether, keto, or thio-ether linkage, etc; Zrepresents nitrogen, oxygen or sulfur or the related elements, seleniumand tellurium, or a radical selected from the group consisting of:

|--ORX); io-R- -X- (-X-(i-X so:); (-R;Sa); (cXN- (RGXN-); (CNN); (RCNN);(-N=N- (NHNH-) which will be hereinafter referred to as group A and inwhich It represents an aryl or an alkyl radical or group and X, X and Xrepresent oxygen or sulfur; 0 represents the number of Z constituentsand is equal to zero or a whole number corresponding to valences on Tnot satisfied with wax, residual hydrogen, or other substituents; Mrepresents at least one hydrogen equivalent of a metal which is eitherdirectly attached to the aryl nucleus T or is attached indirectly to thearyl nucleus T through the atom or group represented by Z; 11 representsthe number of Ms and is always equal to a whole number which, if c is awhole number, is equal to c, it being understood that when 0 equalszero, d must be a whole number so that the composition or moleculerepresented by the above Formula I must contain at least one chemicallycombined hydrogen equivalent of a metal.

In further amplification of the foregoing general Formula I, it will beseen that when 0 is equal to zero, the metallo substituent becomes thehydrogen equivalent of a metal (M) directly attached to the nucleus T,in which event the compound is represented by the formula (wax) n-T-M';also when 0 is a whole number and Z is oxygen or sulfur, the formula forthe composition may be written:

in which X represents oxygen, sulfur, selenium or tellurium and M"represents the hydrogen equivalent of a metal. Instead of including theisolated metal substituent M, the (X"M") substituent, and thesubstituents of group A all under the one representation (ZcMd) as wasdone in general Formula I, I may also represent the group of compoundsor compositions contemplated herein by the general formularepresentation:

in which M'k indicates the hydrogen equivalent of a metal directlyattached to the nucleus T; M indicates the hydrogen equivalent of ametal indirectly attached to T through oxygen or sulfur (X") and Mindicates the hydrogen equivalent of a metal indirectly attached to thenucleus T through Z which may be any one of the radicals listed above ingroup A. The subscripts I0, 1), and s indicate the number of M, (Z'M)and (X"M) substituents, respectively, and are each equal to zero or awhole number corresponding to the valences on T not satisfied by (wax)7r, residual hydrogen, or other substituents, at least one of thesubscripts k, p, or 3 always being equal to a whole number.

As has been previously pointed out, the wax substituent cooperates withthe aryl nucleus to which it is attached in giving pour depressing andV. I. improving properties to the agents contemplated herein. Thissubstituent serves the additional function of solubilizing the compoundor composition as a whole. It is important for the uses contemplatedherein that these metalorganic compounds be oil-miscible; that is,capable of remaining uniformly dispersed in mineral oil either as a truesolution or a colloidal suspension under normal conditions of handlingand use. In this regard there appears to be a critical zone or region inthe degree of wax-substitution below which the compounds or compositionscontemplated herein are not readily soluble in viscous mineral oilfractions. This degree of wax-substitution for an oil-soluble oroil-miscible metalorganic compound of the general type described abovemay vary over relatively wide limits, depending upon whether the arylnucleus is monoor poly-cyclic and whether such nucleus carries othersubstituents, such as hydroxy, alkoxy, aroxy, halogen, nitro, aminoradicals or groups, etc. As indicated above, petroleum wax is thepreferred source of the wax substituent, but it is to be understood thatother equivalent long chain aliphatic hydrocarbon compounds, such asester waxes, may be employed.

As sources for the aryl nucleus which carries the wax substituent I mayemploy any one of a multiplicity of monoor polycyclic, substituted orunsubstituted aromatic compounds.

In general it appears that any metal may be used in the compoundscontemplated herein to provide compositions which have multifunctionalmineral oil-improving properties. Metal substituents which areconsidered particularly useful in these improving agents may be broadlyclassified as the metals belonging to the silver, copper, tin, aluminum,iron, alkali and alkaline earth analytical groups, which include:silver, mercury, lead, and thallium; bismuth, copper, and cadmium;arsenic, antimony, and tin; iron, cobalt, nickel, and manganese; barium,calcium, strontium, and magnesium; and sodium, potassium, and lithium,respectively. Other desirable metals include: titanium, cerium, thorium,vanadium, molybdenum, tungsten, uranium, and platinum.

Exemplary types of compounds falling into the general class contemplatedby this invention are illustrated in the following table in which theformulae given are for illustrative purposes only and show only themonocyclic nucleus which is unsubstituted except for the wax and a metalor a metallo complex substituent.

Table I 1. Wax-aryl-metallo compounds (a) (wax .M

01. bUlVHUDl IIUND, LAQLHHMU Type compound Illustrative general formula.Type compound Illustrative general formula )n EI (b) (wax),.- -R XM V 102. Wax-aryl metal oxides.. (a) (wax)- --0M v A 7. Wax-aryl-ether metal(a) (wax),. X"-RM compounds. A u (b) mm --ROM A V (b) (wax),.- -X"-R-XM3. Metal salts of wax-nryl (a) (wax),. SM X thio acids. '4 20 V (c)(wax),. -XR-- -XM (b) (wax),. RSM 26 (a) (Wax)n-- -X -XM SH 30 \X n 30 ex R-C-XM wa SM G-XM as (won-Q X,

C-RM 8 Wee); 2311!! 5:150 metal (a) (wax) SH 4o (e) (wax)n 0 WM),.--C-R-XM H C-XM SM 45 (c) (wax),, C-RCXM 0') )n-- I V 0 XM IB 5 4. Metal]salts of wax-cry] (a) (wax)- C-XM (d) (WflX)'- ac s. 55 2 1 a )n--R-C-XM O l V 9. Wax-aryl-ester metal (a) (wax)n@C-0-RXM 60 or;compounds. I 5. Metal salts of wax-hy- (a) (wax),,-- -C--XMdroxy-aromatic acids. (b) (wax)n -CO--RM 65 OM (b) (wax),. -C-XM f 0-0K70 x (wa 6. Metal salts of wax-hy- (a) (wax) -g,8XM

droxyaromatic aliphatv lc aclds. ("l-KM Type compound Illustrativegeneral formula Type compound Illustrative general formula 10. Metalsalts of wax-aryl sullonic acids.

DHllIlGS.

12. Metal salts of win-aryl amides.

(wax) (wax)..-

In the foregoing exemplary formulae (wax)n has the same significanceindicated above in connection with general Formula I: X, X and Xrepresent oxygen, sulfur, or the related elements, selenium andtellurium; R represents an aliphatic or an aromatic group which may ormay not be otherwise substituted. R of Formulae 11 and 12 representshydrogen, alkyl, or aryl radicals, and Mm in Formulae 1(0), 11(a)2, (b)2and (0)2 represents double compound metal salts formed by addition ofinorganic salts to aromatic hydrocarbons and to aromatic amines.

It will be observed from the foregoing illustrative examples that all ofthe disclosed compounds are metalorganic compounds or compositions whichare characterized by the presence of a wax-substituted aryl nucleus. Thecompounds falling into the groups indicated by the numerals 2 to 12inclusive may be considered as compounds in which the metal is presentin the radical or group WM in which M represents the hydrogen equivalentof a metal and in which W represents nitrogen, oxygen, sulfur, seleniumor tellurium, or the radicals --SO3- and in which X and X indicateoxygen or sulfur. In part of these typical compounds the radical WM isdirectly attached to the aryl nucleus and in other of these compoundsthe radical WM is attached to adaydrocarbon substituent R which may beeither alkyl or aryl in nature.

Compounds of the type represented by groups 2 and 3 may be considered aswax-aryl metalorganic compounds in which the metal is present in theradical XM where X represents oxygen or sulfur or the related elements,selenium and tellurium, and compounds represented in groups 4 to 9inclusive, which contain either the XM group or the group, may also beconsidered as compounds containing metal in the radical --XM, since thecompounds of these groups which contain the carboxy or thio acid radicalwill also contain the radical XM discussed above because the radical XMforms part of the metallo-carboxy or metallothio acid radical. Compoundsin which the hydrogen of a carboxy or thio acid group is substitutedwith its equivalent weight of metal may be classified as metalorganiccom- 252. UUMPU IHUNS,

fur. It is to be understood that metal attachments to R (where R isaryl) such as M or WM (where W represents nitrogen, oxygen, se-' lenium,tellurium, or (SO3) (CX'X) etc., can also be made on the wax-arylnucleus, further, where R is aryl in the formulae of Table I, it may,bewax-substituted.

In connection with the illustrative examples given in Table I, it is tobe understood that the aryl nucleus may be polycyclic (a nucleus derivedfrom naphthalene, anthracene, diphenyl, etc); also that there may beother substituents in the nucleus than the wax and metal or metallocomplex. In this same regard it should be understood that the waxsubstituent (aliphatic group containing at least twenty carbon atoms)may be polyvalent in nature, in which event each of the polyvalent waxradicals or groups will be attached to a plurality of aryl nuclei, eachof which aryl nuclei has at least one metal or metallo complexsubstituent, and each of which may have attached to it one or moremonovalent wax substituents and may, in addition, have othersubstituents, such as aliphatic hydrocarbon groups containing less thantwenty carbon atoms, hydroxy, alkoxy, aroxy, alkaryl, aralkyl, aryl,halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide,thiamide or thiaroxy radicals or groups, etc.

Where nuclear substituents are present containing methylene groups suchas alkyl, keto, ether, ester, acid radicals, etc., the same may alsocarry substituents such as halogen, hydroxy, amino, nitro, cyanogen,etc. Metal compounds containing thiaroxy substituents are an importantclass. By the reaction of wax-aryl compounds, the metal salts of whichare illustrated in Table I, with sulfur dichloride, hydrochloric acidgas is evolved with the formation of the aryl thio ether compound, Byreaction with sulfur monochloride the disulfides are formed.

Formula I above illustrates the essential requisites of the compounds orcompositions contemplated herein, namely, a wax-substituted aryl nucleusand a metallo complex in chemical combination therewith; and if it isborne in mind that (waxhl may be one or more monovalent or polyvalentaliphatic hydrocarbon groups of at least twenty carbon atoms or amixture of such groups, that T may be otherwise substituted, and that(ZcMd) represents at least one hydrogen equivalent of a metal or ametallo complex containing one such equivalent of a metal, this formulais a fairly accurate representation of the field of compounds orcompositions contemplated herein. To illustrate more completely and moreaccurately the field of invention, taking into consideration thepolyvalent wax type of wax-aryl metalorganic composition and also takinginto consideration the possibility of other substituents in the arylnucleus, I have devised the following general formula:

in which T has the same significance described above under Formula I;(ZcMd) represents at least one metallo atom or one metallo complex ofthe type described in connection with Formula I; R represents at leastone aliphatic or alkyl hydrocarbon (wax) group having at least twentycarbon atoms, such wax group or groups being attached by one valenceonly to at least one aromatic nucleus T; 12 represents the valence ofthe wax radical R", which I have found for best results in obtainingoil-miscible products should be one to four; Yb represents a monovalentelement or group, such as residual hydrogen, which may be replaced withan aliphatic radical or group containing less than twenty carbon atoms,hydroxy, alkoxy, aroxy alkaryl, aralkyl, aryl, halogen, cyanogen, nitro,nitroso, amino, keto, ester, aldehyde, amide, thiamide or thiaroxyradicals or groups, etc.; 1) represents the number of Ybs and is equalto zero or a whole number corresponding to the valences on the nucleus Tnot satisfied with R or (ZcMd) and e represents a whole number from oneto four and indicates the total number of groups (T- (Yb) (ZcMd))present in the molecule represented by the formula which are attached tothe aliphatic group or groups represented by R".

In the foregoing general Formula II it will be seen that the compoundsrepresented thereby include those materials in which all of the .waxsubstituent (RF) is monovalent (0:1 and e=1) or in which all of the waxsubstituent is polyvalent (v and e being equal to two, three or four) orsince R. is defined as being at least one and may therefore includeseveral such groups, it will be seen that this general Formula II isinclusive of compounds having aliphatic groups or radicals of difierentvalences (from one to four) in the same molecule. Also, it will beobserved that since e may be any whole number from one to four, thenumber of aromatic nuclei T in the molecule may likewise vary from oneto four. It will be seen, therefore, that the relationship between e andv in Formula II in its broadest aspect is such that when e is equal toone, 12 is equal to one, and when e is greater than one, the valence vof at least one of the R s is equal to e in order to tie the severalnuclei or Ts together, the valence of any remaining R s being any wholenumber equal to or less than c.

The more simple types of compounds coming under general Formula II inwhich 12 and e is each equal to one and in which there is only one waxsubstituent R may be illustrated by the following formula showing T forpurposes of illustration as a monocyclic nucleus:

there are two such monovalent R" groups, may be represented by thefollowing formula:

H H H 11 HO --C C --OH H H H H in which the chain and substituentcharacters have the same significance defined above.

Compounds of the type satisfying general Formula II in which R ispolyvalent and v and e are more than one and in which there is only onesuch polyvalent R group may be illustrated by the following formula inwhich the aryl nucleus T is again indicated for illustration as beingmonocyclic:

(Z=M.1) (ZMa) (Z=Md) Yr-i- Yr- Yb H \l/ H H0 "o --o --c -CH H H H H HUnder this same type of compound indicated by Formula C there may alsobe more than one R (wax) group (represented by the chain), such compoundin which there are, for example, two polyvalent R. groups beingillustrated by the following formula in which the characters have thesame significance described above under Formula C:

H H H H HC--C "OH I (ZJWJ) (ZBMJ) d) H HG "C "CH have the samesignificance as in the formulae above.

H H H H 11% -C --C --C -CH /L =Md) I (ZZM.1) I C d) H H Y5 I Y's-p IY1,- --C- -"CH n H H y I II no --o --o -01! H II II It As to the numberof R" (wax") groups going to make up a single molecule, this will varywith the extent to which it is desired to effect substitution of thenucleus with the wax derivatives for obtaining the desired properties inthe product aromas and is, 01 course, limited by the number ofreplaceable hydrogens on the aromatic nucleus which are available forsubstitution. As will be apparent to those skilled in the art, themaximum number of R groups which can be attached to a single aromaticnucleus will vary as the nucleus is monoor polycyclic and also as thenucleus is otherwise substituted. It will also be apparent thatreplaceable hydrogens on the nuclei may all be substituted withpolyvalent wax substituents.

It will be understood that the oil-improving agents contemplated by thisinvention may be pure compounds satisfying the general Formula II abovewith a monoor poly cyclic nucleus as T and with or without one or moreof the various Yb substituents. However, in manufacturing the preferredoil-improving products of this invention by procedures in whichwax-substitution is eiTected with a chlorinated wax by the Friedel-Crafts reaction, the final oil-improving product is normally or usuallya mixture of difierent compounds corresponding to different values of cand v and to different numbers of wax groups R".

Since the wax-aryl metalorganic compounds or compositions describedherein are contemplated for use as oil-improving agents, it is importantthat the wax substituent comprise a sufiicient proportion of thecomposition as a whole to render the same miscible with mineral oilfractions under normal conditions of handling and use. The amount of waxsubstituent to accomplish this will, as stated above, vary underdifferent conditions; but, as a general guide, it appears that bestresults are obtained if the percentage of wax contained in the Wax-arylconstituent calculated as a wax-aromatic compound otherwiseunsubstituted is not substantially less than eighty per cent.

Instead of grouping the various possible metal substituents under oneradical (ZcMd) as was done in general Formula II, this same type offormula may be employed, indicating the possible metal-bearingsubstituents with the radicals Mk, (ZM) and (X"M")s, which have the samesignificance described above in connection with general Formula I. Thismodification of general Formula II may be written as follows:

Illustrative procedures which may be followed in synthesizing typicalcompounds or products fallin into the various type compoundclassifications of Table I will now be described. It is again emphasizedthat while Table I shows only monocyclic aromatic derivatives, bothmonoand polycyclic compounds are contemplated herein; and that where theterm wax is used, I have reference to any equivalent aliphatichydrocarbon having at least twenty carbon atoms or organic compositionspredominantly comprised of such high molecular weight aliphatichydrocarbons.

TYPE CoMPoUNn 1 Wax-aryl-metallo compounds illustrated under Example 1,Table I, may be prepared by (a) the Grignard reaction or (b) reaction ofwax-aryl compounds with alkali metals in the presence of aliphaticethers.

The Grignard reaction may be used for the synthesis of various metalcompounds other than those of the alkali group. It is well known thataromatic halogen derivatives with the halogen in the nucleus or sidechain react in dry ethereal 252. COMPOSITIONS,

or hydrocarbon solution with magnesium metal to form organo magnesiumcompounds, such as RMgBr and RCHz-MgCl, for example, where R is aryl.These metallo compounds, known as Grignard reagents, can be used in thesynthesis of other metal compounds by reaction with a halide of thedesired metal whereby double decomposition takes place to form magnesiumhalide and the desired metallo derivatives.

For the synthesis of Type 1 compounds illustrated as (a) and (b) inTable I, wax benzene is to be first prepared, followed by chlorinationat low temperature in the dark to efiect chlorination of the nucleus insynthesis of 1(a) or by chlorination at about 200 F. in the presence oflight or carriers such as iodine to produce chlorination of the wax orlower alkyl group in the synthesis of compounds of the 1(b) type.

The formation of the Grignard reagent (waxaryl-magnesium compounds) isto be carried out in the same manner for Type compounds 1(a) and 1(b),followed by reaction with a halide of the desired metal to form thewax-aryl-metallo compound.

Alkali metal compounds of Type 1 Wax naphthalene, for example, isreacted with alkali metal in a proportion of one atomic weight of alkalimetal for each mole of wax naphthalene in the presence of an aliphaticether such as dimethyl ether, the mixture being agitated at atemperature below the boiling point of the ether until solution of thealkali metal takes place.

TYPE COMPOUND 2 Typical compounds or products belonging torepresentative members of the general class of wax-aryl metalorganiccompositions typified by the formulae of group 2 in Table I togetherwith illustrative methods for synthesizing these products will bedescribed in thefollowing examples:

A parafiin wax melting at approximately F. and predominantly comprisedof aliphatic hydrocarbon compounds having at least twenty carbon atomsin their molecules was chlorinated by melting the wax and bubbling thechlorine therethrough until it had absorbed about sixteen per centchlorine, such-product having an average composition between a monochlorwax and a diohlor wax. A uantity of this chlorwax containing threeatomic proportions of chlorine was thenreacted with one molecularproportion of phenol (CcHsOI-I) in the presence of aluminum chloride toform a wax-phenol having a phenol content in the neighborhood of aboutthirteen per cent. After purification to remove all unreacted phenolthis wax-phenol was reacted with finely divided metallic sodium at atemperature of 500 F. with rapid stirring and in the presence of anon-oxidizing gas to form a wax-substituted sodium phenate.Wax-substituted potassium phenate may be prepared by following the sameprocedure, using a temperature of 400 F., the reaction being completedin a one-hour period. Examples of the reacting proportions which may beused in the synthesis are as follows:

Parts by weight (a) Wax-phenol (13.2% c o m b i n e d phenol) 500 Sodiumor equivalent amount of potassium 16 (b) Wax-naphthol (15.7% c o m b ine d naphthol) 500 Sodium or equivalent amount of potassium 12% exam m6!Wax-substituted aryl oxides of the alkali or alkaline earth metals andmetals from the silver, copper, aluminum, tin, and iron analyticalgroups can also be prepared by the reaction of the waxhydroxyaromaticcompound (wax-phenol) with an alcoholate of the desired metal, thereaction mixture being heated to about 300 F. during a one-hour period.The alcohol is distilled off during the reaction, thereby obtaining awax-substituted aryl metal oxide as the finished product. Anhydrousmethyl and ethyl alcohols are considered preferable for preparing thealcoholates for use in this reaction.

The wax-aryl lead oxide (wax-substituted lead phenate) can be readilyprepared by reacting wax-phenol with litharge in the presence of anon-oxidizing gas and heating the mixture with stirring to a temperatureof about 500 F. during a one-hour period.

It will be observed that the phenol content of the wax-phenol used inthe preparation of wax phenates was given above as being in theneighborhood of thirteen per cent. I have found that as a generalproposition where wax-phenols having a phenol content substantiallygreater than thirteen per cent are employed in the preparation of thewax phenates (wax-substituted aryl metal oxides), products of thedesired solubility in viscous mineral oils do not appear to be readilyobtained. It may be said, therefore, as a general proposition that thepreparation of wax-substituted aryl metal oxides according to theprocedures outlined above should be carried out with wax-substitutedhydroxyaromatic com pounds in which the ratio of hydroxyaromaticcompound to wax-substituted hydroxyaromatic material is notsubstantially greater than the chemical equivalent of thirteen per centphenol.

TYPE COMPOUND 3 The type compound represented by Formula 3(a) is to beprepared by the reaction of a waxaromatic compound with sulfurmonochloride to form a disulfide, followed by reduction to form themercaptan.

Naphthalene, for example, is to be reacted with a chlorwax of aboutsixteen per cent chlorine content in the presence of anhydrous aluminumchloride. By use of the aluminum chloride catalyst in a concentration ofabout ten per cent by weight in respect to naphthalene, a triwaxnaphthalene can be prepared by heating the reaction mixture to about 300F. and holding at this temperature during a one-hour period.

Reaction mixture Grams Chlorwax 200 Naphthalene 45.6 A1C13 4 Thereaction product is to be purified by washing with water to remove thealuminum chloride, thereafter separating the water and drying themixture to obtain the finished wax naphthalene. The. operation ofwater-washing can be facilitated by the use of diluents such as benzoland using alcohol to break the emulsions. The diluent will also be anaid in drying the product, as

complete removal of water will be effected during the distillation ofthe diluent.

The wax naphthalene is then to be reacted with sulfur monochloride inthe following proportions at about F. to form the disulfide:

V Moles Wax naphthalene; 2

Sulfur monochloride SzClz 1 The disulfide is to be reduced to themercaptan by treating with reducing agents such as tin or iron in thepresence of hydrochloric acid, stirring the mixture vigorously tofacilitate the reducing action by improved contacting of the mixturewith nascent hydrogen.

The product may then be neutralized with aqueous sodium hydroxidesolution to form the sodium mercaptide. The mixture can be dried to givethe finished alkali metal salt; or the aqueous mixture can be reactedwith aqueous solution of a polyvalent metal salt, stirring the mixtureat about 175 F. during a one-hour period to obtain the polyvalent metalmercaptide. The product is to be purified by water-washing to removereaction salts, followed by separation of the water and drying to givethe finished product.

TYPE COMPOUND 4 Example 1 Wax-aromatic acids of type 4(a) wherein X andX represent oxygen are to be prepared from wax-aromatic hydrocarbons bydifferent procedures:

1. By formation of a ketone followed by oxidation of the keto group to acarboxyl radical by reaction with oxidizing agents such as alkalihypochlorites or permanganates.

2. By direct oxidation of, an alkyl group to COOH.

3. By chlorination of the aromatic nucleus of the wax-aromatichydrocarbon, followed by reaction with sodium and C02.

The preferred procedure consists in formation of a keto product,followed by oxidation. A triwax benzene is to be formed by theFriedel-Crafts reaction described in example of Type compound 3 information of wax naphthalene. Without purification of the Friedel-Craftsreaction product, acetyl chloride, for instance, is to be introduced inan amount to form a monoor diketo product, heating the mixture withstirring at about F., using a chlorinated solvent such as ethylenechloride to reduce the viscosity of the mixture.

The ketone may then be purified by washing with water to remove thealuminum chloride, followed by refluxing with sodium hypochlorite forseveral hours and stirring vigorously to effect the oxidation of theketo group to carboxyl. The use of a hydrocarbon diluent such as benzolwill be desirable in this reaction to reduce the viscosity of themixture. The free acid may then be obtained by neutralizing the mixturewith mineral acid. The wax aryl acid thus formed is neutralized with analcohol solution of sodium hydroxide to form the sodium salt.

The polyvalent metal salts can then be prepared by double decompositionof. the sodium salt with an equivalent amount of the desired polyvalentmetal salt in aqueous or non-aqueous medium according to proceduresherein outlined.

When the alkali metal salts are to be isolated rather than used asintermediates in the formation of the salts of polyvalent metals, theymay be prepared by neutralization of the wax acid with alcoholicsolution of alkali hydroxide, distilling the water of reaction andalcohol to give the finished product.

Example 2 Wax-aryl aliphatic acids, the salts of which are illustratedin Type compound 4(1)) of Table I,

wherein X and X represent oxygen, have been prepared by the reaction ofa wax-aromatic hydrocarbon with an unsaturated aliphatic acid such asoleic acid; or with a chloraliphatic acid such as chlorstearic acid.

A wax naphthalene, for example, prepared by procedure described underType compound 3, is condensed with oleic acid, for instance, by use ofanhydrous aluminum chloride as a catalyst, using an amount of aluminumchloride sufiicient to neutralize the carboxyl group, and heating themixture at about 300 F. to bring about the formation of the aluminumsalt of the wax-aryl aliphatic acid. The free acid is then obtained bywashing the mixture with aqueous hydrochloric acid to decomposecompletely the aluminum salt.

The polyvalent metal salts are prepared by neutralizing the free acidwith aqueous sodium hydroxide solution (20% NaOH) and then reacting withan equivalent of an aqueous solution of a salt of the desired metal,stirring the mixture at about F. during a one-hour period to completethe formation of the polyvalent metal salt. The product is purified bywater-washing to remove reaction salts, separating the water and dryingto obtain the finished product.

The reaction of double decomposition between the alkali metal salt andthe salt of the desired polyvalent metal can also be carried out innonaqueous medium. In this case the wax-aryl acid is neutralized withalcoholic alkali hydroxide or with a sodium alcoholate (alcoholateprepared preferably from amyl or lower alcohol). The reaction mixture isheated to about 300 F. and held at this temperature about one hour,allowing the alcohol to distil to give the finished alkali metal salt.The mixture is then treated with an alcohol-soluble salt of the desiredpolyvalent metal in an amount equivalent to the alkali metal salt,thereafter adding about ten per cent by volume of amyl alcohol andrefluxing at about 240 F. during a one-hour period to complete thereaction.

The polyvalent metal salt can be purified by filtering, centrifuging orwater-washing to remove the reaction salts.

Chlorinated or hydrocarbon solvents such as. tetrachlorethane, Stoddardsolvent and toluene may be used during the preparation and purificationof the salts to reduce the viscosity of the mixture, in which case thediluent is finally distilled to give the finished product.

Because of emulsions formed in the preparation of alkali salts inaqueous medium, it is preferred to prepare such compounds by thereaction of the wax aryl acids with alkali alcoholates (alcoholatesformed preferably from amyl or lower alcohols), heating the reactionmixture to about 300 F. during a one-hour period and allowing thealcohol to distil to obtain the finished salt.

The alcoholate method, as described under the preparation of wax-arylmetal oxides of polyvalent metals (Type compound 2), may also be used inpreparing the carboxylates of polyvalent metals of type compoundsillustrated in Table 1.

Example 3 Thio acids such as thiolic acid; the salts of which arerepresented by Type formula 4(a), wherein X represents oxygen and Xrepresents sulfur, are to be prepared by the reaction of wax aryl acidchlorides with sodium sulfide, followed MPUSITIONS,

by neutralization of the alkali salt with mineral TYPE COMPOUND Example1 A wax-phenol or a wax-substituted hydroxyaromatic compound having acombined phenol content in the neighborhood of from thirteen per cent tosixteen per cent is prepared and converted into the wax-aryl metal oxideor the wax phenate of an alkali metal in the same manner described underType compound 2 above, after which it is carboxylated according to theKolbe synthesis (passing CO2 through the compound or a solution thereofat elevated temperature (350 F.) and either atmospheric orsuperatmospheric pressure) to form the alkali metal salt of thewax-substituted hydroxyaromatic carboxylic acid. This salt constitutesone of the products or improving agents contemplated by this inventionand the corresponding salts of other metals may be formed from thealkali metal salt by a process of double decomposition with thealcoholsoluble inorganic or fatty acid salt of the desired metal.Products of this synthesis are typical of the Type compounds 5(a) inTable I.

Example 2 With a wax-substituted hydroxyaromatic carboxylic acid of thetype obtained in Example 1 as a starting material the metal saltswherein both the hydroxyl and the carboxyl groups are substituted withmetal may be obtained by reacting the hydroxyaromatic salt of Typecompound 5(a) with an alcoholate of the desired metal, thereby replacingthe hydroxyl hydrogen with such metal. Salts of this last-mentioned typemay be obtained in which the metal substituent in the hydroxy group isthe same metal as or a different metal from the metal substituent in thecarboxy group. Salts of this type, which I may term wax-substitutedmetaloxyaromatic-metal carboxylate salts, are typical of Type compound5(b) in Table I.

TYPE COMPOUND 6 Example 1 A wax-phenol having a combined phenol contentof about thirteen per cent is reacted withan unsaturated aliphatic acidsuch as oleic acid in the presence of anhydrous aluminum chloride. Byuse of an amount of aluminum chloride equivalent to both the hydroxylgroup of the phenol examine:

about two parts of benzol and neutralizing with aqueous sodium hydroxidesolution (20% NaOH), thereafter forming the polyvalent metal salt bydouble decomposition with an equivalent amount of the desired metal saltin aqueous solution. The reaction of double decomposition can becompleted by stirring the mixture about an hour at 175 F., thereafterwater-washing the product to remove completely the reaction salts anddistilling the benzol to obtain the finished product.

Products of this example are typical of Type compound 6 (a) in Table I.

Example 2 Type compounds 6(b) of Table I wherein both the hydroxyl andcarboxyl group are substituted with metal can be obtained by reactingthe metal salt of Example 1 with an alcoholate of the desired metal,whereby the hydroxyl hydrogen is replaced with metal. Salts of this typecan be prepared in which the metal substituent of the carboxyl group isunlike the metal substituent in the hydroxyl group. Compounds of thistype are termed wax-substituted metaloxyaromaticmetal carboxylate saltsof wax-hydroxy-aryl aliphatic acids.

TYPE CoMPoUNn 7 Example 1 Wax-sodium phenate is prepared from waxphenolof about sixteen per cent combined phenol content according to theprocedure described in the preparation of Type compound 2. Sodiumchloracetate is then prepared by slowly adding to an alcohol solution ofchloracetic acid, a standard alcoholic solution of sodium hydroxide,keeping the temperature of the reaction mixture below 100 F. The sodiumchloracetate is then added to the wax-sodium phenate, the reactionmixture being held at a temperature of 150 F. during a two-hour period.By diluting the mixture with an appropriate diluent such as Stoddardsolvent the mixture can be centrifuged or filtered to remove reactionsalts, thereafter removing the diluent by distillation to obtain thesodium salt of a wax-phenyl ether acid as the final product.Corresponding salts of other metals may be prepared by reacting thesodium (or other alkali metal or an alkaline earth metal) salto'f theether acid with an alcohol-soluble inorganic or fatty acid salt of thedesired metal at a temperature of 175 F. over a two-hour period.

It will be understood, of course, that the sodium or other alkali metalsalts of other chlororganic acid may be used in the first. step of thisprocedure to obtain other ether acid salts or oxy-alkyl acid saltsubstituents on the aryl nucleus.

Products of this example are typical of Type compound 7(a) in Table I.

Example 2 The salts of aryl-xanthic acids illustrated by Type formula7(a), wherein X" is oxygen and X and X represent sulfur, can be preparedfrom the reaction product of wax-alkali phenates with carbon disulfide.

A triwax-phenol, for example, formed by the reaction of phenol withchlorwax of nineteen per cent chlorine content, is reacted with sodiumethylate, the mixture being heated to 300 F. and held at thistemperature about an hour to form the wax-sodium phenate. By reaction orthe phenate with carbon disulfide in a pressure bomb,

heating at about 200 F. during a one-hour period, the wax-aryl sodiumxanthate is formed. The product of this reaction is soluble in mineraloil.

Any of the wax-alkali-aryl xanthates can be formed by this reaction bythe modification of preparing the wax phenates of the desired alkalimetal. The polyvalent metal salts can be prepared by doubledecomposition of the alkali salt with a salt of the desired polyvalentmetal, the reaction being carried out in aqueous or nonaqueous medium.

Example 3 Another example of Type formula 7(d) Wherein X", X and Xrepresent oxygen, is found in the reaction of a wax-alkali phenate withCO2. This product is an intermediate in the formation of the alkalisalts of wax-phenolic acids illustrated by Type formula 5(a).

In the reaction of wax-sodium phenate with CO2, the wax phenate is firstconverted into a product (identified as the intermediate represented by7(cl)), which is highly resilient when cool but which changes uponfurther reaction to a more fluid product, the latter being identified asthe sodium salt of wax-phenolic acid. The intermediate product isusually designated as an alkali-aryl carbonate, but conducts itself in amanner similar to the aryl ether acids in rearranging to givehydroxyaromatic acids of Type formulae 5(a) and 6(a).

TYPE COMPOUND 8 Example 1 Metal salts of keto acids can be prepared fromwax acids formed by the condensation of waxaromatic or wax-substitutedmixed aromatic hydrocarbons with anhydrides of dibasic acids, ofaliphatic, cycloaliphatic or aromatic type. Examples of mixed aromatichydrocarbons are phenols, aromatic ethers, and heterocyclic compounds.

Naphthalene, for example, is condensed with chlorwax of about sixteenper cent chlorine content by procedure above outlined and condensed withphthalic anhydride in the presence of aluminum chloride, using thefollowing proportions:

Moles Wax-naphthalene 1 Phthalic anhydride 1 Aluminum chloride 2 Thewax-naphthalene and phthalic anhydride are mixed together and dissolvedby addition of a chlorinated solvent such as tetrachlorethane,thereafter adding the aluminum chloride in small portions at a time at'room temperature. The reaction temperature is then raised to 200 F. andthe mixture stirred for several hours to complete the reaction.

In the formation of the polyvalent metal salts, the reaction mixture iswashed with water containing sufficient mineral acid to remove thealuminum and neutralized with aqueous sodium hydroxide solution; anequivalent amount of an aqueous solution of a salt of the desiredpolyvalent metal is then added, the reaction and purification beingcarried out by procedures herein outlined.

Example 2 In Example 1, which illustrates a method of preparation ofType compound 8(0), the aromatic nucleus to which the carboxylateradical is attached is not wax-substituted. Type compound 8(d) is anexample of a wax-substituted aromatic nucleus to which the carboxylateradical is directly attached. In preparing this latter type of productwax-benzene, for instance, is to be converted to a diketo product byreaction with an acid chloride such as acetyl chloride, as describedunder preparation of compounds of Type 4 (a). Mixed ketones are to beformed also by use of both aliphatic and aromatic acid chlorides. Thediketo product is to be partially oxidized to give the desired keto acidfrom which the metal salts may be prepared. R of Formula 8 ((1) will bealkyl when an aliphatic acid chloride only is used in formation of thediketo product; R will be aryl when a mixed aliphatic-aromatic diketoproduct is formed in the synthesis of keto acids.

TYPE COMPOUND 9 Example 1 Wax-aryl ester metal compounds represented byFormula 9 (a, b, c) are to be prepared from the reaction products ofwax-aromatic acids with alcohols. Compounds 9 (a, b) are to be preparedfrom esters formed by the reaction of monobasic wax aryl acids withmonoor dihydric alcohols; Compound 9 (c) from acid esters of wax-aryldibasic acids and monohydric alcohols.

Compound represented by 9 (c), for example, is to be prepared by thereaction of a wax aryldicarboxy acid with sufficient aliphatic oraromatic monohydric alcohol to form the acid ester, thereafterneutralizing with sodium hydroxide solution to form the alkali salt,followed by reaction with a salt of the desired polyvalent metal inaqueous or non-aqueous medium by procedures herein outlined to form thepolyvalent metal salt.

Example 2 The wax-aryl ester metal compounds represented by Formula 9(d, e, 1) have been prepared from the reaction products of wax-phenolsand wax phenolic acids with aliphatic or aromatic acid chlorides.Compounds 9 (d, e) are prepared from esters formed by the reaction ofwax-monoand polyhydric phenols with monobasic acid chlorides; Compound 9(I) from acid esters of wax phenolic acids and monobasic acid chlorides.

Compounds represented by 9 (j), for example, may be prepared by thereaction of wax phenolic acid with acetyl chloride, for instance, toform the acid ester. The acid ester is then neutralized with alcoholicalkali hydroxide to form the alkali salt as one product of thisinvention. The salts of polyvalent metals are then prepared by doubledecomposition of the alkali salt with a salt of the desired metal inaqueous or non-aqueous medium to form the polyvalent metal salt.

TYPE COMPOUND 10 Metal salts represented by Type formulae 10 (a) and 10(0), wherein R. is aryl, are to be prepared from the sulfonic acidsresulting from the sulfonation of wax-aromatic hydrocarbons, waxphenolsor wax-aryl ethers.

Compounds represented by Type formulae 10 (b) and 10(0), wherein R isalkyl, are to be prepared by the halogenation of wax-aromatic compoundswhereby the side chain is substituted, followed by reaction with alkalisulfite to form the wax-aryl-aliphatic sulfonates.

The polyvalent metal salts are to be prepared by the reaction of thealkali salt with an in- 2oz. UUIVIPUSI HONS, a lilfll 5 A e e a et od othe fo at on of Metal compounds wherein a valence of a polypollnds of yp11 Consists in e formation of valent metal is satisfied by a hydroxylgroup conmetal salts of aromatic amines resulting from m t basic metalcompounds The method of the nitration d following reduction of formationconsists in the use of one extra equivaa a yd s, wax-hyd y r at lent ofalkali hydroxide in the neutralization of hydrocarbons, and wax-aromaticethers. Nitrath free ax acid, followed by treating with a 10 tion o enucleus followed y reduction Will amount of polyvalent metal saltequivalent to the give arylamines; reduction of nitro groups present 11i hydroxide d, in side chains will result in the formation of wax-DOUBLE COMPOUNDS FROM WAX-ABOMATIO Coluaryl'ahphatlc ammes' room) WITHBIETAL HALIDE AN METALS 15 Metal compounds of the (a, b, c)1 type can beS 8 D 15 formed from the alkali metals, substituting one It has beenpreviously pointed out that double or both of the hydrogens of the aminogroup compounds can be formed with metal halides and with metal.aromatic amines (Type compounds 11(CL)2, (1292,

Metal compounds of the (a, b, 0)2 type are and (0)2. Likewise, doublecompounds can be formed from inorganic salts such as ZnClz, COClz,formed by an addition reaction of wax-aro- 20 HzPtClc, HAuCla, etc.,wherein straight addition matic compounds with metallic halides such asto the amino group takes place to form double stannic chloride, aluminumchloride, etc. The compounds. V Grignard reagents above described areexamples By the well-known procedure of diazotization, of additioncompounds formed by the reaction of the wax-arylamines are to beconverted to the aryl halides with metals. Further, the alkali 25 diazoc p n s which may be represented y metals form metal salts with aromaticcomthe gro p (N=N) Because of the alkaline pounds by an additionreaction, giving derivatives nature of the diazo compounds, double saltscan of the double compound type. It is to be underbe formed by e ionWith inorganic metal salts stood, therefore, that the present inventioncon- (--N=N-MHe). templates waX-aryl metallo compounds of both 30 Byreactions w w to the art, the product the addition and substitution typeas multiresulting from the reaction of diazotization may functional mial oil-improving agents. be converted to compounds of the generalformula Numerous compounds or compositions falling (N=NA) whe ein A y bewithin the broad general class contemplated (S B (CX' from Which metalSalts herein have been synthesized and tested in min- 35 can be derived(N=N'SO3 eral oil fractions of the viscous or lubricant type N=N-CXXM).and all of them have been found to be possessed y reduction of theproduct of diazotizetion of multifunctional oil-improving properties iny diaZonium chloride) in acid medium the that they all have beendefinitely proved to effect 40 W 37 hydrazines are to be formed, havingimprovement in at least two of the following 4 (--N'I-INH) as acharacteriz ng p- The properties, namely, pour point, viscosity index,ClPaZlneS are known to form Salts of the type of and inhibition ofoxidation. All of the composithe eryleminestions which have been testedfor all three prop- TYPE COMPOUND 12 erties have been found to beimproving agents Wax-aryl amides, the metal salts of which are all hTllese l p be used in 45 illustrated by Type formulae 12, are to beviscous mineral oil fractlons in varying amounts pared from wax-aryl andwax-aryl ether acids rangmg m oneslxteenth P t E ten per by the generalmethod of formation of the acid cent dependmg upon condltlqn ofchlorides followed by treating with ammonia. etc., and Table II below isrepresentative of the The thiamides can be formed from the amides bynumer 011s waxaryl-metano compositions which 50 reaction with P2S5 havebeen prepared and tested to demonstrate the The amides and thiamides areknown to be efficacy f the n r l class of compounds nd tautomeric inform, whereby two types of metal compositions contemplated by thisinvention. salts (a, b, oh and 2 are possible. In one type (a, b, c) 1the amino hydrogen is substituted with Table II v 55 metal; in the (a,b, (2)2 type the substitution Cuprio Salt of Wax-phenol oarboXyllo eoldwith metal takes place in the OH or SH group, Aluminum salt ofWax-phenol carboxylic acid leaving the nitrogen valence (R) satisfiedwith Zino Salt of waX-phenol oalboxyllo fie hydrogen alkyl, or arylradica1s Chromic salt of wax-phenol carboxyllc acid (30 Amidines f thegeneral formula Ferric salt of wax-phenol carboxylic acid 50 are to beprepared from the amides or thiamides Cobaltous Salt of Wax-PhenoloarboXylio a by replacement of oxygen or sulfur with NH or MangaIlOv-SSalt of Wa -p f y acid NR (R being alkyl, aryl, OH, etc.) using methodsCalcium salt of wax-phenol carboxyllc acid familiar to the art. Wherehydrogen is substi- Magnesium Salt of WaX-Phenol carboXylio acid G5tuted with an OH group amidoximes are formed \VPQtaSSlUm salt ofWax-phenol carboxylic acid CNNOH) Salts of the amine type can be Sodiumsalt of wax-phenol carboxylic acid prepared from the amidines' Cobaltsalt of wax-pheno1 carboxylic acid Sodium salt of Wax-beta naphtholcarboxylic acid NEUTRAL ACID AND BASIC METAL SALTS OF Sodium salt ofwax-alpha naphthol carboxylic ARYL COMPOUNDS acid 70' In the foregoingdiscussion, methods have been Wax-lead phenate a given for thepreparation of neutral metal salts, Wax-stannous phenate but it is to beunderstood that acid and basic Wax-aluminum phenate metal salts ofcompounds represented by Type Wax-zinc phenate l5 formulae 2-12 are alsocontemplated. Wax-calcium phenate 15 organic salt of the desired metalin aqueous solution by procedures above outlined.

TYPE COMPOUND 11 Metal compounds wherein one or more acid groups, suchas phenolic OH, mercaptan, SH, carboxy or thiolic groups, etc., remainunsubstituted are considered as acid metal salts.

Wax-potassium phenate nitrogen, sulfur, oxygen, selenium, tellurium,Wax-sodium phenate (SO3), (-CXN), (-CNN), and Wax-sodium betanaphtholate Wax-sodium alpha naphtholate I Wax-sodium phenate-sodiumcarboxylate salt Wax-cupric phenate-sodium carboxylate saltWax-Cobaltous phenate-manganous carboxylate salt Wax-cobaltousphenate-cobaltous salt Wax-stannous phenate-stannous carboxylate saltWax-stannous phenate-cobaltous carboxylate salt Wax-ferric phenateferriccarboxylate salt Zinc salt of wax-phenyl-methyl carboxy ether acidCobaltous salt of wax-phenyl-methyl carboxy ether acid Dicobaltous saltof dicarboxy wax phenolic acid Cobaltous salt of wax-naphthyl-stearicacid Cobaltous salt of wax-hydroxy-phenyl stearic acid Cobaltous salt ofwax-naphthoyl benzoic acid Wax-phenyl sodium xanthate All of theproducts enumerated in the above table can be broadly identified asoil-miscible metalorganic compounds or compositions which arecharacterized by the presence of a wax-substituted aryl nucleus. In someof these products the metal is present as a metallo-complex directlyattached to the aryl nucleus, and in others it is present in a sidechain (ether acid, aryl aliphatic acid, etc.) substituent. All of thecompounds listed above satisfy and come under general Formulae I, I andII, II. It is to be understood that certain of these compounds orcompositions may be preferred for use in certain mineral oil fractionsand certain of the compounds or compositions may be preferred to others,depending upon the conditions or properties which are to be improved,but it is, as stated above, a characteristic of all of these products orcompositions that they have multifunctional oilimproving propertieswhich may vary in magnitude, etc., with the oil and the constituents ofthe compounds. Some of the compounds or compositions or sub-groups ofcompounds or compositions may be preferred to others from the standpointof cost, ease of synthesis, odor, color, etc., but it is not myintention in the present application to draw any preferentialdifferentiation or distinction between the various subgroups, since theyare being made the subject matter of additional applications. It isemphasized, therefore, that the invention is not limited by the specificexamples or illustrative procedures described above but includes withinits scope such variations and modifications as fairly come within thescope of the appended claims.

I claim:

1. A mineral oil composition comprising: a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound characterized by the presence carboxylate "of a wax-substitutedaryl nucleus.

in which X and X represent oxygen or sulfur.

3. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound characterized by the presence of a wax-substituted arylnucleus, at least part of the metal in said compound being present inthe radical XM in which M represents the hydrogen equivalent of a metaland X represents elements from the group consisting of sulfur andoxygen.

4. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound characterized by the presence of a wax-substituted arylnucleus, at least part of the metal in said compound being present inthe radical in which M represents the hydrogen equivalent of a metal andX and X represent elements from the group consisting of oxygen andsulfur.

5. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound characterized by the presence of a wax-substituted arylnucleus, at least part of the metal in said compound being present inthe radical ZM attached to said wax-substituted aryl nucleus and inwhich M represents the hydrogen equivalent of a metal and Z represents aradical selected from the group consisting of nitrogen, sulfur, oxygen,selenium, tellurium:

in which R represents a hydrocarbon group and X, X, and X" representradicals selected from the group consisting of oxygen and sulfur.

6. A mineral oil composition comprising a viscous mineral oil fractionand in admixture therewith an oil-miscible metalorganic compound whichis characterized by the presence of a wax-substituted aryl nucleus, saidmetalorganic compound being present in an amount sufficient to improvethe oil in at least two of the following respects: improvement of pourpoint; improvement of viscosity index; and inhibition of oxidation.

'7. A mineral oil composition comprising a viscous mineral oil fractionand in admixture therewith from about one-sixteenth per cent to aboutten per cent of an oil-miscible metalorganic compound which ischaracterized by the presence of a wax-substituted aryl nucleus.

8. A mineral oil composition comprising a viscous mineral oil fractionand in admixture therewith from about one-sixteenth per cent to aboutten per cent of an oil-miscible metalorganic compound which ischaracterized by the presence of LUL: UUIVIFUOI l IUHO an aryl nucleushaving part of its nuclear hydrogen substituted with petroleum wax.

9. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of a metalorganic compound whichis characterized by the presence of a waxsubstituted aryl nucleus and inwhich said wax substituent-comprises a sufiicient proportion of saidcompound to render same miscible with said oil fraction under normalconditions of handling and use.

10. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound characterized by the presence of a wax-substituted arylnucleus, at least part of the metal in said compound being present inthe radical -WM in which M represents the hydrogen equivalent of a metaland W represents a radical selected from the group consisting of sulfur,oxygen, and the radical x! in which X and X represent element selectedfrom the group consisting of oxygen and sulfur, said radical -WM being asubstituent in said aryl nucleus.

11. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of a metalorganic compound havingthe general formula:

wherein: T represents an aromatic nucleus; (ZcMd) represents a metallosubstituent which is attached to said aromatic nucleus and wherein: Zrepresents a radical selected from the group consisting of nitrogen,sulfur, oxygen, selenium, tellurium, and

in which R. represents a hydrocarbon group and X, X and X" representelements selected from the group consisting of om'gen and sulfur; Mrepresents the hydrogen equivalent of a metal; 0 is equal to zero or awhole number; and d is a whole number which, when 0 is a whole number,is equal to 0; Yb represents a monovalent radical selected from thegroup consisting of allphatic hydrocarbon radicals having less thantwenty carbon atoms, hydroxy, alkoxy, aroxy, aralkyl, alkaryl, aryl,halogen, cyanogen, nitro, nitroso, amino, keto, ester, aldehyde, amide,thiamide, and thiaroxy radicals; 1) represents the number of Ybs and isequal to zero or a whole number corresponding to the valences on T notsatisfied by R or (ZcMd) R, represents at least one aliphatic group ofat least twenty carbon atoms having a valence v of one to four andattached by one valence only to at least one nucleus T; and e is a wholenumber from one-to four.

12. A mineral oil composition comprising a mineral oil fraction and inadmixture therewith a minor proportion of a wax-aryl metalorganiccompound having the general'formula:

in which T represents an aromatic hydrocarbon radical selected from thegroup consisting of monocyclic and polycyclic aryl, aralkyl,hydroxyaryl, halogen-aryl, amino-aryl, nitro-aryl, and diaryl radicals;(wax) represents aliphatic hydrocarbons characterizing wax attached tothe aryl nucleus T; n represents the number of wax groups and is equalto a whole number corresponding to valences on T not satisfied byresidual hydrogen or other substituents; M represents the hydrogenequivalent of a metal directly attached to the nucleus T; (X"'M")represents, a metallo complex directly attached to the nucleus 'I inwhich M" is the hydrogen equivalent of a metal and X represents anelement from the group consisting of oxygen, sulfur; selenium, andtellurium; (ZM)represents a metallo complex attached to the nucleus Tand wherein M is the hydrogen equivalent of a metal and Z repre sents aradical selected from the group consisting of:

(-NHNH-), -oNN-), -RoNN- in which R represents a hydrocarbon group, andX, X and X" represent elements selected from the group consisting ofoxygen, sulfur, selenium, and tellurium; and k, p, and s are subscriptsindicating the number of M, (Z'M) and (X"'M) substituents respectivelyand each is equal to zero or a whole number corresponding to thevalences on the nucleus T not satisfied by residual hydrogen or othersubstituents, at least one of the subscripts lc, p, or s always beingequal to a whole number.

ORLAND M. REIEF.

DISCLAIMER -.:5:';;:;" 2,197,835.0rland M. Rez'fi, Woodbury, N. J.MINERAL OIL COMPOSITION. Patent 3 dated April 23, 1940. Disclaimer filedJuly 16, 1942, by the assignee,

Socony-T acuum Oil Company, Incorporated. Hereby disclaims the followingsubject matter from each of the claim patent: A mineral oil fractionhaving in admixture therewith a minor proportion of a metal salt of awax-substituted aromatic sulfonic acid.

[Oflicial Gazette August 25, 1942.]

n s m sald 1 v CERTIFICATE.OF CORRECTION. Patent No. 2,197,855. April2;, 191m.

ORLAND M. REIFF.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 15first column, line 25, claim 10, for the words "an element read"elementsand that the said Letters Patent shouldbe read with thiscorrection there-' in that the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 18th day of March, A. 1). 191m.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

DlSCLAlMER 2,197 ,835.Orland M Reifl, Woodbury, N. J. MINERAL OILCOMPOSITION. Patent dated April 23, 1940. Disclaimer filed July 16,1942, by the assignee, Socony-T acuum Oil Company, Incorporated. Herebydisclaims the following subject matter from each of the claims insaidpatent:

A mineral oil fraction having in admixture therewith a minor proportlonof a metal salt of a. wax-substituted aromatic sulfonic acid.

[Ofliciql Gazette August 25, 1942.]

